190. Phthalocyanines. Part XII. Experiments on the preparation of tetrabenzporphyrins

Linstead, R. P.; Noble, E. G.

doi:10.1039/jr9370000933

Cited by 11 publications

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“…The following year, Robertson confirmed the structure and aromaticity of the phthalocyanine macrocycle by X-ray diffraction [4]. Subsequently, Linstead developed general methods for the synthesis of various phthalocyanine precursors, in particular, o-dinitriles [5][6][7][8], metal phthalocyanines [9][10][11][12][13], substituted phthalocyanines [14,15], and their analogues [16][17][18][19][20][21][22][23].…”

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confidence: 94%

Out-of-Plane Coordinated Zirconium(iv) and Hafnium(iv) Phthalocyaninates

Chernii¹,

Tretyakova²,

Tomachynska³

et al. 2021

Ukr. Chem. Journ.

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The article is devoted to methods of synthesis, the structure, and spectral characteristics of zirconium and hafnium phthalocyaninates with out-of-plane coordinated ligands. The general scheme for the synthesis of out-of-plane coordinated Zr and Hf phthalocyanines includes obtaining initial dichloride or dihydroxo complexes, which then undergo substitution reactions with -dicarbonyl compounds, hydroxybenzoic, sulfo- and aliphatic carboxylic acids, etc. In the case of polyphenols, which are bidentate ligands, one ligand is coordinated to the central atom of the macrocycle. If -dicarbonyl compounds or carboxylic acids are introduced into the reaction, two ligands are coordinated. The reactivity of the out-of-plane coordinated ligands of Zr and Hf phthalocyanines was also investigated. In all obtained out-of-plane coordinated Zr and Hf phthalocyanines, the ligands are located in the cis position relative to the plane of the phthalocyanine macrocycle. X-ray diffraction, NMR, and UV-Vis spectroscopy have proved this arrangement of ligands. According to the X-ray diffraction data of Zr and Hf dibenzoylmethanato phthalocyanines, the metal atom is out of the plane of the phthalocyanine macrocycle, which itself is not planar. The central atoms are located almost in the middle between the N4 planes of the phthalocyanine macrocycle and the O4 of the extraplanar ligands. The UV-Vis spectra of out-of-plane coordinated Zr and Hf phthalocyanines in organic solvents have a typical appearance for most metal phthalocyanines, characterized by a B-band of absorption in the region of 335–350 nm, a Q-band at 680-690 nm, and its satellite in the region of 615–620 nm. If the extraplanar ligand is a chromophore (e.g., curcumin or condensed derivatives of dehydroacetic acid), there are additional absorption bands in UV-Vis spectra located between the B- and Q-bands. The influence of the nature of the central metal atoms, ligands and solvents on the fluorescent properties of the out-of-plane coordinated Zr and Hf phthalocyanines was also discussed.

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confidence: 94%

Out-of-Plane Coordinated Zirconium(iv) and Hafnium(iv) Phthalocyaninates

Chernii¹,

Tretyakova²,

Tomachynska³

et al. 2021

Ukr. Chem. Journ.

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“…In 1930s and 1940s, Linstead and co-workers reported the preparations and UV-Vis spectral data for a number of porphyrin and phthalocyanine complexes, including zinc phthalocyanine (ZnPc) and zinc tetrabenzoporphyrin (ZnTBP) molecules, in a series of papers. [1][2][3][4][5][6] Since then, lots of experimental and theoretical investigations were performed, initially because of their central role in biological processes such as respiration and photosynthesis, 7 more recently because of their potential technological applications, [8][9][10] including photovoltaic and solar cells, 11 molecular electronics and photonics, nonlinear optics, [12][13][14] photodynamic therapy, 15 and so on. These highly stable macrocyclic π -systems display interesting properties such as optical stability and efficient light absorption in the near-infrared and visible region of the spectra that make them potential candidates for applications in optoelectronics, photo conducting materials.…”

Section: Introductionmentioning

confidence: 99%

Franck-Condon simulation of vibrationally resolved optical spectra for zinc complexes of phthalocyanine and tetrabenzoporphyrin including the Duschinsky and Herzberg-Teller effects

Guo

Dai

et al. 2012

The Journal of Chemical Physics

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High resolved absorption and fluorescence spectra of zinc complexes of phthalocyanine (ZnPc) and tetrabenzoporphyrin (ZnTBP) in the region of Q states were reported. Few theoretical investigations were performed to simulate the well-resolved spectra and assigned the vibrational bands of the large molecules, especially for high symmetrical characteristic molecules, on account of the difficulties to optimize the excited states and analyze a large number of final vibrational-normal modes. In the present work, the S(0) ↔ S(1) absorption and fluorescence spectra (that is, the Q band) of ZnPc and ZnTBP were simulated using time-dependent density functional theory with the inclusions of Duschinsky and Herzberg-Teller contributions to the electronic transition dipole moments. The theoretical results provide a good description of the optical spectra and are proved to be in excellent agreement with experimental spectra in inert-gas matrices or in supersonic expansion. This study focused attentions on the optical spectral similarities and contrasts between ZnPc and ZnTBP, in particular the noticeable Duschinsky and Herzberg-Teller effects on the high-resolved absorption and fluorescence spectra were considered. Substitution of meso-tetraaza on the porphyrin macrocycle framework could affect the ground state geometry and alter the electron density distributions, the orbital energies that accessible in the Q band region of the spectrum. The results were used to help interpret both the nature of the electronic transitions in Q band region, and the spectral discrepancies between phthalocyanine and porphyrin systems.

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“…Tetrabenzoporphyrin (TBP) has a similar skeletal alignment as phthalocyanine, which is one of the most common and useful dyes. TBP was first prepared from carboxymethylphthalide under harsh conditions (345–420 °C) by Linstead and Noble in 1937 1. Recently, TBP and phthalocyanine derivatives have attracted considerable attention as organic semi‐conducting materials for field‐effect transistors (OFET),2 near‐IR dyes,3 nonlinear optical materials,4 and as photosensitizers for photodynamic therapy (PDT) of cancer tissues 5.…”

Section: Introductionmentioning

confidence: 99%

First Synthesis of meso‐Chlorinated Tetrabenzoporphyrins

et al. 2009

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Keywords: Porphyrinoids / Halogenation / Aromatic substitution / Dyes/Pigments / Cleavage reactions meso-Chlorinated bicyclo[2.2.2]octadiene-fused porphyrins 2 (Cl n TBCODPs; n = 1-4) have been synthesized by chlorination of the free base TBCODP-H 2 (1-H 2 ) using N-chlorosuccinimide (NCS). The chlorinated derivatives were easily separated by column chromatography on silica gel to give 2-H 2 in good yields. This method for the chlorination of porphyrin using NCS is mild, safe, and economic compared with the established procedure for the meso-chlorination of porphyrins. We also discovered the unexpected meso-chlorination of the porphyrin with dichlorodicyanobenzoquinone (DDQ) by single-electron transfer. Cl n TBCODPs 2 were converted into tetrabenzoporphyrins (Cl n TBPs) 3 in 100 % yields by retro-Diels-Alder reaction. The derived compounds were characterized by NMR spectroscopy, UV/Vis spectrophotom-

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190. Phthalocyanines. Part XII. Experiments on the preparation of tetrabenzporphyrins

Cited by 11 publications

References 0 publications

Out-of-Plane Coordinated Zirconium(iv) and Hafnium(iv) Phthalocyaninates

Out-of-Plane Coordinated Zirconium(iv) and Hafnium(iv) Phthalocyaninates

Franck-Condon simulation of vibrationally resolved optical spectra for zinc complexes of phthalocyanine and tetrabenzoporphyrin including the Duschinsky and Herzberg-Teller effects

First Synthesis of meso‐Chlorinated Tetrabenzoporphyrins

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